The current state of socio-economic development, characterized by a radical change in the technical and technological paradigm in a globalized world, is marked by new phenomena and processes. In contrast to previous eras, when the formation of new technological methods of production was based on a small number of breakthrough inventions that changed the structure of production, today we observe an avalanche-like development of inventions, the products of which destroy the stability of all spheres of society. Accordingly, all resources possessed by a modern company must meet the requirements of the time in terms of their quality. Under such conditions, not only intellectual capital but also other components, that enable companies to maneuver in their innovative development, become very important. Based on the analysis of modern conceptual approaches to determining the essence of the categories “structural capital” and “intellectual capital”, the article forms the concept of “national structural capital”. The latter is presented as an infrastructure for the formation, implementation and development of national human capital, an organizational and institutional system for the expanded reproduction of knowledge and skills of members of society. For the quantitative measurement of national structural capital, a methodological framework is proposed, which is based on the integral index of national structural capital created by the authors; its components are justified: knowledge & technology outputs, intangible assets, research & development (R&D), knowledge workers, knowledge absorption. Based on the proposed methodology for determining the integral index of national structural capital, its value was calculated for 26 countries for 2018-2020 and the dynamics for the period under study were shown.